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Cesium carbonate → tert-butyl 4-(1-(4-methoxybenzyl)-5-phenyl-1H-pyrazolo[3,4-b]pyridin-4-yl)piperazine-1-carboxylate

HRID 387557
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HRID 387557 반응식
Br[C:2]1[C:3]([N:20]2[CH2:25][CH2:24][N:23]([C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])[CH2:22][CH2:21]2)=[C:4]2[CH:10]=[N:9][N:8]([CH2:11][C:12]3[CH:17]=[CH:16][C:15]([O:18][CH3:19])=[CH:14][CH:13]=3)[C:5]2=[N:6][CH:7]=1.[C:33]1(B(O)O)[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1.C([O-])([O-])=O.[Cs+].[Cs+]>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O.CCOCC>[CH3:19][O:18][C:15]1[CH:14]=[CH:13][C:12]([CH2:11][N:8]2[C:5]3=[N:6][CH:7]=[C:2]([C:33]4[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=4)[C:3]([N:20]4[CH2:21][CH2:22][N:23]([C:26]([O:28][C:29]([CH3:31])([CH3:30])[CH3:32])=[O:27])[CH2:24][CH2:25]4)=[C:4]3[CH:10]=[N:9]2)=[CH:17][CH:16]=1
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HCID 10796Cesium carbonateHCID 66827Phenylboronic AcidHCID 68760849tert-butyl 4-(5-bromo-1-(4-methoxybenzyl)-1H-pyrazolo[3,4-b]pyridin-4-yl)piperazine-1-carboxylate

생성물 1

HCID 68764155tert-butyl 4-(1-(4-methoxybenzyl)-5-phenyl-1H-pyrazolo[3,4-b]pyridin-4-yl)piperazine-1-carboxylate수율 89%

시약·촉매·용매 4

HCID 178418397
HCID 178418397, 화합물
촉매
HCID 962Water용매2회
HCID 3283Diethyl Ether용매
HCID 312751,4-Dioxane용매

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온도
80 °C

실험 절차

tert-Butyl 4-(5-bromo-1-(4-methoxybenzyl)-1H-pyrazolo[3,4-b]pyridin-4-yl)piperazine-1-carboxylate (0.50 g, 0.995 mmol), phenylboronic acid (0.182 g, 1.49 mmol), Pd(PPh3)4 (0.115 g, 0.0995 mmol) and Cs2CO3 (1.30 g, 3.98 mmol) were placed in dioxane:H2O (8 mL, 3:1). The solution was heated to 80° C. for 6 hours. Ether (50 mL) and H2O (20 mL) were then added. The organic layer was separated, washed with brine, dried over sodium sulfate, filtered and concentrated. The resulting residue was purified by column chromatography (DCM:ethyl acetate=5:1) to give tert-butyl 4-(1-(4-methoxybenzyl)-5-phenyl-1H-pyrazolo[3,4-b]pyridin-4-yl)piperazine-1-carboxylate (0.442 g, 89%) as a foam solid. MS ESI (+) m/z 500.4 detected. 1H NMR (400 Hz, DMSO-d6) δ 8.26 (s, 1H), 8.10 (s, 1H), 7.51 (m, 2H), 7.44 (m, 2H), 7.32 (m, 1H), 7.20 (d, J=8.4 Hz, 2H), 6.83 (d, J=8.4 Hz, 2H), 5.50 (s, 2H), 3.67 (s, 3H), 3.23 (m, 4H), 3.20 (m, 4H).

후처리

  1. customThe organic layer was separated
  2. washwashed with brine
  3. dry with materialdried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe resulting residue was purified by column chromatography (DCM:ethyl acetate=5:1)

출처 및 근거

ORD 기록
ord-4279ab9a99914cc69a893358804e84e4
출처 데이터셋
uspto-grants-2013_02
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US08372842B2

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